Process for producing carboxylic acids

ABSTRACT

A PROCESS FOR PRODUCING STRAIGHT CHAIN UNSUBSTITUTED MONABASIC CARBOXYLIC ACIDS HAVING FROM ABOUT 7 TO ABOUT 19 CARBON ATOMS PER MOLECULE WITH IMPROVED SELECTIVITY BY OXIDATION OF SELECTED OLEFINS. ALPHA OLEFINS ARE DIMERIZED TO PRODUCE ETHYLENES CONTAINING AT LEAST 1,1DISUBSTITUTION WITH A METHYLENE GROUP IN THE ALPHA POSITION OF AT LEAST ONE OF THE SUBSTITUTING RADICALS. THE ETHYLENES ARE OXIDIZED SELECTIVELY TO PRODUCE CLEAVAGE OF THE MOLECULE AT THE LINKAGE OF THE METHYLENE GROUP OF THE RADICAL TO THE BALANCE OF THE SUBSTITUTED ETHYLENE MOLECULE.

PROCESS FOR PRODUCING CARBOXYLIC ACIDS Gene C. Robinson, Baton Rouge,La., assignor to Ethyl Corporation, New York, N.Y., a corporation ofVirginia No Drawing. Continuation-impart of application Ser. No.

460,558, June 1, 1965. This application Oct. 29, 1968,

Ser. No. 771,670

Int. Cl. C08h 17/36 US. Cl. 260-413 3 Claims ABSTRACT OF THE DISCLOSUREA process for producing straight chain unsubstituted monobasiccarboxylic acids having from about 7 to about 19 carbon atoms permolecule with improved selectivity by oxidation of selected olefins.Alpha olefins are dimerized to produce ethylenes containing at least1,1- disubstitution with a methylene group in the alpha position of atleast one of the substituting radicals. The ethylenes are oxidizedselectively to produce cleavage of the molecule at the linkage of themethylene group of the radical to the balance of the substitutedethylene molecule.

CROSS REFERENCE TO RELATED APPLICATION This application is acontinuation-in-part of application Ser. No. 460,558, filed June 1,1965, now abandoned.

BACKGROUND OF THE INVENTION Field of the invention This inventionrelates to the production of straight chain unsubstituted monobasiccarboxylic acids having from about 7 to about 19 carbon atoms permolecule. In greater particularity, the invention relates to theselective production of acids having a narrow range of molecular weightof compounds in a given product mixture so as to facilitatepurifications and separations of product acids and to provide enhancedeconomics in producing specific desired product acids and narrowmolecular weight range mixtures having fairly closely related similarproperties. The process employs oxidation of sensitized olefins havingsensitivity to oxidative attack and cleavage at only a few particulardefinite points in the molecule brought about 'by a molecularconfiguration characterized by the presence of a side chain having morethan one carbon atom attached to a carbon atom which forms a part of theolefinic double bond linkage of the molecule. Typical olefins that areuseful in such an oxidation are those characterized as vinylideneolefins and tri-substituted ethylenes, particularly thosetri-substituted ethylenes having methyl as one of the substitutinggroups of the 1,1- positional substitutions.

Description of the prior art The oxidation of hydrocarbons to producevarious oxygenated materials, particularly carboxylic acids, has beenexplored for many years. Prior efforts in this line have encountered thevery serious fundamental difficulties that the selectivity ofconventional partial oxidation operations with hydrocarbons, evenolefins, is very poor. In particular, with saturated hydrocarbons thepoint of oxygen attack upon the carbon atoms of the molecule is notlimited to any specific carbon atom. Since the conversion of an alkanemolecule to carboxylic acid after an initial attack on an internalcarbon atom generally involves cleavage in the hydrocarbon moleculeinvolved, the result is that, for the most part, each hydrocarbonmolecule oxidized to acid produces two or more short chain acids andthese can vary in number from formic acid all the way to the maximumnumber of carbon atoms per molecule in the feed employed or obtained.

United States Patent Thus, if one were to seek, for example, theproduction of a particular acid or of a narrow range of acids, saydodecanoic, tridecanoic, and tetradecanoic, having generally similarproperties in certain desired uses, such as detergent or cleaning soapmaterials, one finds that the yield of the desired acids is quite smallin terms of weight of desired acids produced per unit weight of feedhydrocarbon. The foregoing lack of selectivity of oxidation is generallysimilar with unsaturated molecules even olefins of straight chain carbonskeleton configuration. In general, there may be a minor sensitizationof certain carbon atoms in some ordinary olefinic molecules; however, asa practical matter such a sensitization is normally so small as to bevirtually insignificant in ordinary types of operations under commerciallarge scale conditions.

Another disadvantage of prior hydrocarbon oxidation connection with thelack of selectivity of oxidation of molecules such as of alkanehydrocarbons, is the production of difunctional molecules such as ketoacids, hydroxy acids, and dibasic acids due to the occurrence of attackson several carbon atoms of individual hydrocarbon molecules. Althoughsuch difunctional molecules may be desired in some instances, they arenot normally desired when the production of monocarboxylic acids of highpurity is sought because esterification occurs between the carboxylicacid groups and the hydroxy groups and various condensations involvingcarbonyl groups are likely to occur. The results of such molecularcombinations is the loss or difiicult recovery of materials of thedesired product range due to the formation of heavy molecules of estersand the like which are difiicult to resolve into desired product rangecomponents.

It is of course well known that various kinds of hydro carbons,unsaturated as well as saturated, have been subjeoted to oxidation suchas outlined in the foregoing. Olefins seemingly present certainadvantages in obtaining some selectivity due to the double bond;however, with the type of ordinary olefins used in prior art oxidationsit is almost as difiicult to obtain low cost olefins which are pure asregards location of the double bond as it is to obtain selectivity ofoxidation of alkane molecules. Alpha olefins can be relatively pure butthey are costly. Although numerous direct dehydrogenation processes areknown, and there are others which involve various manipulation sequencessuch as halogenation of alkanes followed by dehydrohalogenation, oroxidation of alkanes to secondary alcohols followed by dehydration,there is always the question of selectivity. As a practical matter, oneshould be prepared to expect a random distribution as to the location ofolefinic double bonds resulting from such processes and therefore as tothe molecular weight of product carboxylic acids resulting from theoxidation of such.

Although the direct dehydrogenation of alkanes was introduced in theforegoing paragraph as a source of olefins, normally this process is notvery attractive particularly when dealing with hydrocarbons having fromabout 10 to 20 carbon atoms per molecule because in addition to a lackof selectivity of the point of dehydrogenation, unless the olefinsproduced are removed from the dehydrogenation mass as soon as they areformed. which is difficult, there is a high probability that additionaldehydrogenation of the monoolefins will occur producing molecules withvarious forms of multiple unsaturation such as acetylenes and diencs. Itwill be readily recognized that the oxidation of dienes will producecleavage at two points in the molecule resulting in the production of ahigher percentage of acids of short chain length.

SUMMARY The process of the present invention provides highly selectiveproduction of monobasic carboxylic acids of straight chain carbonskeletal configuration ranging from about 7 to about 19 carbon atoms permolecule. Although this broad range is set forth, it is characteristicof the selectivity capabilities of the process of the present inventionthat by appropriate choice of starting olefin, homologous series productacid mixtures are produced which involve predominantly a selected spreadof only about 4 or 5 carbon atoms per molecule. As a practical matterwhen starting with a typical pure olefin such as decene-l, thendimerizing and oxidizing according to the present process, acidspredominating in those having from 7 to 11 carbon atoms per molecule areobtained. In another illustration with another pure typical olefinstarting material, octadecene-l, dimerization and oxidation inaccordance with the teachings of the present invention provides straightchain monobasic carboxylic acids predominating in those having from 15to 19 carbon atoms per molecule. For intermediate molecular weightolefins, substantially the same relationships between molecular weightof starting olefins and of product acids are realized.

Where the starting olefin is a mixture of olefins as typified forexample by a mixture of decene-l and octadecene-l, the dimerizationproducts include combinations of the different molecular weight olefins.In general, the oxidation of such results in two spectra of acids beingproduced, one corresponding to the products of each olefin as a pureolefin. Thus to follow through with the illustration, where a typicalmixture of decene-l and octadecene-l is employed for dimerization andthe dimerization product is oxidized, the acid products predominate inone spectra having from 7 to 11 carbon atoms per molecule and anotherspectra having from 15 to 19 carbon atoms per molecule.

To expand the illustration using 3 or more olefins of differentmolecular weight in the starting olefins employed for dimerization,additional spectra of acids are obtained. Thus where one feeds threetypical olefins, decene-l, tetradecene-l and octadecene-l, one obtainsacids ranging from 7 through 19 carbon atoms per molecule.

The information of the preceding paragraphs is summarized in thefollowing equation representations.

18 carbon atoms per molecule. C=carbon atom, hydrogens being omitted.

Isomerization of vinylidene dimer RCOC=C ROC=OC RCCC-C R'C o R"C o RC oREARRANGING FORMULAS AND ADDING SIGNIFICANT H ATOMS A genericrepresentation of the foregoing proximately branched olefin is:

wherein:

R =methyl radical or straight chain alkyl radical having from about 7 toabout 18 carbon atoms per radical.

R =straight chain alkyl radical having from about 7 to about 18 carbonatoms per radical.

R =H, methyl radical or straight chain alkyl radical having from about 7to about 18 carbon atoms per radical.

With the proviso that when R is straight chain, R is methyl.

The foregoing olefins preferentially tend to produce mainly R R and Racids plus R 0, R C, R C and R CC acids. In many instances the one andtwo carbon atom fragments evolve as non-acid molecules and in any eventare not in the desired product range. Thus limited, highly selective,product acid spectra are obtained.

Where dimerization is employed, an R of 18 corresponds to a C startingolefin.

[Carbon Atoms in Principal Product Range Acids] Starting olefin todimerization Tetra- Octa- Decene-l deeene-l decene-l Acid skeleton:

RG C7 C11 C15 C12 C16 C13 11 C13 C1 C14 C18 C15 10 RCCCOOH, RCCCCOOH,and RCCCCCOOH Particularly preferred product acids and oxidizing olefinsare those wherein the product acids are predominantly in the C to Crange and R and R are straight chain alkyl radicals having from about 10to about 14 carbon atoms per radical and R is hydrogen. The foregoingpreferred olefin is preferably pure or in admixture with olefins whereinR is methyl radical and R and R are straight chain alkyl radicals havingfrom about 10 to about 14 carbon atoms per radical.

Another preferred oxidizing olefin is one wherein R and R are straightchain alkyls having more than 10 but not more than 14 carbons and R ishydrogen or a straight chain alkyl having up to 18 carbons.

The oxidizing of the foregoing olefins to produce acids is carried outat a temperature from 75 C. to about C.

OBJECTS It is accordingly an object of the present invention to providea process wherein a low cost readily producible oxidation feed stock isemployed which imparts selectivity to the oxidation process and whichreadily oxidizes at selected points at comparatively low temperatures atwhich oxidations at non-selected points cannot occur.

Another object of the present invention is to provide a process wherebyolefins possessing a high uniformity of structure can be obtainedreadily and which oxidize with a high degree of selectivity.

Another object of the present invention is to provide a process wherebycertain branched chain olefins, the product of a particularlyadvantageous processing sequence, can be oxidized with high selectivityto produce straight chain monocarboxylic acids.

Other and further objects and features of the present invention willbecome apparent upon a careful consideration of the followingdescription of certain preferred embodiments of the present invention.

DISCUSSION In accordance with the teachings of the present invention, aprocess is provided whereby olefins obtainable for example by directdehydrogenation or other suitable processes such as chain growth,polymerization, halogenation-dehydrohalogenation and the like areconvertible to dimerized olefins which are oxidized readily to producein high yield straight chain monobasic carboxylic acids of selectedmolecular weight. The dimerized olefin configurations apparently aremuch more readily oxidized near the center of the molecule than othermaterials because of the fact that these molecules contain a double bondplus branching in proximity to the double bond plus at least onemethylene carbon atom adjacent to the branching. These olefins containat least the 1,1-disubstituted configuration, at least one of the lsubstitution radicals containing a methylene carbon atom in the alphaposition. The following illustrates the nature of these olefinconfigurations.

C=CH2 and R-C=CHR ROHZ (1) (2) (vinylidene (flirt-substituted Olefin)Olefin) (1,1-disubstituted ethylenes) where the R groups are straightchain alkyl and may be different. The desirability for the methylenecarbon atom effectively eliminates molecules where the R groups are allmethyl. The amount of isomers of the tri-substituted dimer having thedouble bond at positions other than the above should be kept small inthose instances where minimum formation of branched acids is desired asis explained further at a subsequent point of the specification. It hasbeen discovered that such dimerized olefins will oxidize with greatselectivity at the sensitized alpha carbon of the alkyl radicals, themethylene carbon adjacent to the branching, to produce almostexclusively chiefly four sizes of oxygenated materials, a first pairwhich has a quantity of carbon atoms per molecule which is equal to thenumber of carbon atoms in the alkyl groups on the far side of the carbonatoms linked by the double bonds, the second pair which includes theadjacent linked carbon atom with one of the alkyl groups of thedimerized olefins. Once such a molecule begins, the selective oxidation,then the cleavage as described follows the unique pattern, The fifthsize of oxygenated materials, frequently disregarded, arises from the1,1,2-tri-substituted ethylenes.

In greater particularity, a typical vinylidene dimer, also called a1,1-disubstituted ethylene, whose parent vinyl olefin components havethe same number of carbon atoms (RCC=C) has the configuration i RCCOCCRwhere both R groups have the same number of carbon atoms. This oxidizesto produce chiefly RCOOH,

RCCOOH, RCCCOOH and RCCCCOOH acids within the relationships of thisparagraph.

The availability of suitable vinylidene and tri-substituted olefins insufiicient purity for this oxidation is an immediate problem becauseuntil now, olefins of such structure have largely been regarded asundesired byproducts of certain polymerizations or of chain growthaccording to Ziegler technology where one seeks to produce vinyl olefinsand they are not readily obtainable directly from petroleum or othernatural sources of hydrocarbon types of materials. It has beendiscovered, however, that random olefins are readily isomerized to alphaolefins (even if only momentary) in a catalytic environment such as withtriisobutyl aluminum at temperatures from about 250 C., more preferably100- 200 C., typically C., and that without specifically requiring thenormally very difficult separation of alpha olefins from the reactionmass, the alpha olefins only will dimerize in the same environment toproduce vinylidene olefins of the long chain length desired. Onenormally views this reaction itself as being undesirable because itinvolves an isomerization environment and even the vinylidenes isomerizeto the tri-substituted form which one would not expect to be desirableoxidation feed to produce straight chain acids. In this instance it hasbeen discovered that surprisingly the tri-substituted olefins arevirtually as suitable as oxidizer feed as are vinylidene olefins, andthat mixture of such dimers are quite suitable for selective oxidation.

The starting olefins used for dimerization can be pure as regards numberof carbon atoms per molecule or they can be mixed, depending uponvarious factors such as source, cost and the like. With mixed olefinsthe dimer olefins are less symmetrical in terms of length of the Rgroups than with pure starting olefins. If the source of the internalolefins is dehydrogenation of saturated hydrocarbons, an importantadvantage of the combination of such into an overall process is that itis not necessary to remove the unreacted saturated hydrocarbons from thedehydrogenation effluent prior to the combinedisomerization-dimerization treatment. The only separation needed is apost-dimerization separation which is relatively easy because the dimershave virtually double the molecular Weight of the unreacted paralfinsand nondimerized olefins and are therefore readily separated bydistillation so that the non-dimerized materials can be reprocessed.

Numerous advantages of the foregoing dehydrogenation-isomerization-dimerization-oxidation process are immediatelyapparent because this process provides a method of readily obtaininghigh molecular weight olefins which oxidize selectively and difficultseparations of isomers are not required.

In addition to this advantage, the selective oxidation of dimer olefinsoccurs under much milder conditions than the usual non-selectiveoxidation of saturated hydrocarbons so that conditions can be used inwhich nondirected oxygen attacks are virtually avoided. This bringsabout a remarkable reduction in the amount of difunctional moleculesproduced which has numerous beneficial results in subsequentpurification steps. Specifically, esterifications and variouscondensations are largely avoided and the only unsaponifiables presentin the oxidate are mainly unoxidized olefin dimers, allylic alcohols andhydroperoxides all of which have virtually as many carbon atoms permolecule as the desired longer chain product acids, simplifyingunsaponifiable separation considerably.

In the isomerization of random olefins, alpha olefins are normallyproduced readily; however, they do not remain but isomerize back tointernals. The equilibrium mixture is undesirably low in alpha olefins.The dimerization technique provides a way of grabbing the alpha olefinsbefore they revert to the internal form because only these alpha olefinswill dimerize. The dimer is ini- 7 tially a vinylidene type olefin(l,1-disubstituted ethylenes):

however, this olefin is itself subject to isomerization with the doublebond moving to a position adjacent to the R or RC group. This producesthe tri-substituted ethylenes The equilibrium mixture is about percentvinylidene and 80 percent tri-substituted.

Thus a dimer feed for oxidation will range between all vinylidene, whereone removes the dimers virtually as fast as they are formed so as toreduce the formation of tri-substituted olefins, up to the 20 percentvinylidene equilibrium mixture. All of the possible ratios oxidize toabout the same result with the tri-substituted form producing a slightlywider range of acids, but all are straight chain.

The foregoing is subject to a limitation in that the trisubstituteddimers of the foregoing, such as C-CII3 R'C also will isomerize totri-substituted olefins with the double bond no longer adjacent thetertiary carbon atom, such as (with a single H shown for clarity). Thisolefin will oxidize but not as readily as the preferred types under thespecified conditions; however, it will produce a significant quantity ofbranched acids and where this is undesired, the dimer isomerization isnot permitted to continue for such extended periods that would permitany significant quantity of this latter type of olefin to be formed.

As oxidation catalysts, one may use various conventional systems such astertiary butyl hydroperoxide, man ganous stearate, of about 0.1 to about1.0 percent, mixtures of 0.1 weight percent of cobalt orcobalt-containing material and an equal molar amount (cobalt to bromine)of bromine or bromine-containing material such as cobalt acetate andammonium bromide, cobalt bromide, cobalt naphthenates, etc. In additioncopper and vanadium salts, organic as well as inorganic, may be used.

One will note that the oxidation is performed at low temperatures, suchas from about 75 to about 110 C. at which temperatures non-directedattacks on random carbon atoms are virtually avoided. A typicalpreferred temperature is about 105 C.

In certain instances the oxidation is advantageously performed in inertdiluent media, typical reasonably inert diluents being acetic acid andpropionic acid.

In addition to the foregoing discussion of catalytic oxidation, chemicaloxidation using strong oxidants such as nitric acid with vanadiumcatalyst, oxides of nitrogen, and the like are beneficial in someinstances, in all cases however conditions are controlled so as toprovide reasonable rates for directed or selective oxidation andinsignificant rates for the more difficult non-selective or randomoxidations.

Typical olefins oxidized in accordance with the present invention, alkylradicals listed being normal.

R1 R2 R Typical name 001731 Ootyl H 2-octyl decene-l.

o Nonyl H 2-octyl undecene-l. Do Decyl H 2octyl dodecene-l. Undecyl H2-octyl tridecene-l. Dodecyl. H 2-octyl tetradecene l. Tridecyl H2-octyl pentadecene-l. Tetradecyl. H 2-octyl hexadecene-l. Do PentadecylH Z-ootyl heptadecened. Do Hexadecyl H 2-octyl octadecene-l. DoHeptadecyl H 2-octy1 nonadecene-l. Do Octadecyl H 2-octyleicoseSne-1.

R1 R2 R3 Typical name Methyl"-.. Octyl Heptyl Q-methyl heptadecene-S.

D0 Octadecyl Octadccyl ZO-rnethyl octatn'acontene-IQ.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Example 1 Thirty parts ofZ-n-butyl-l-hexene of 99 percent purity was oxidized with oxygen at 106C. for approximately 4 hours. Tertiary butyl hydroperoxide (1 percent)was added at the start. Approximately 20 percent of the olefin reacted.To this mixture was added 1 percent manganous stearate and oxidationcontinued for approximately 5 hours at approximately 106 C. when thetotal olefin oxidized was approximately 75 percent of the startingamount.

The product had an acid number of 5 6.

The acids were extracted with a 7 percent sodium carbonate solution. Thesodium carbonate extract was extracted twice with ether and acidifiedwith HCl. The acids were extracted with ether and the extract distilledto remove the ether.

The resulting crude acids which were of a light straw color wereanalyzed by vapor phase chromatography yielding major amounts ofn-propionic acid (52 weight percent), normal butyric acid (12.6percent), normal pentanoic acid (9.3 percent) and normal hexanoic acid(11.4 percent) with no other major peaks.

The crude acids were 10 percent by weight of the starting material andcorresponded to an average molecular weight of 100.

In this experiment, identification of major products was of main concernand the overall yield was not of great significance.

Example 2 To a stirred reaction flask was added 31.0 grams oftetradecene dimer percent vinylidene plus tri-substituted), 25 grams ofglacial acetic acid and 0.3 grams manganous stearate. This mixture wasoxidized for 14 /2 hours at about 106 C. Oxygen uptake was slow for thefirst half hour, rapid during the next two hours, and

tapering olf to virtually zero during the balance of the period.

36.3 grams of reaction product (exclusive of acetic acid) was recovered.This product was 33.7 percent fatty acid (weight), with 75 percent ofthose acids falling in the (311-015 range.

Example 3 To a stirred reaction flask was added 48.5 grams oftetradecene dimer of Example 2 and 0.5 gram of manganous stearate. Thismixture was oxidized for 12 /2 hours at 106 C. The crude oxidate weighed52.0 grams, and was 17 percent crude acids. Of the crude acids 43 weightpercent was fatty acids (straight chain saturated monofunctionalcarboxylic acids) with 36 percent of the crude or 84 percent of thefatty acids falling in the range of 11 to 15 carbon atoms per molecule.Distribution by carbon atoms per molecule was as follows:

Example 4 To a stirred reaction flask was added 40.6 grams of decenedimer. This material contained 30 percent vinylidene olefin and 70percent of tri-substituted olefin Acid (carbon atoms per molecule):

Weight percent 1.3 3.1 8.2

Example 5 Example 4 is repeated using mixed decenes as feed forconcurrent isomerization-dimerization with similar results.

Example 6 A mixture of decane and decenes resulting from dehydrogenationof decane is subjected to concurrent isomerization and dimerization at188-200 C. under autogenous pressure for 20 hours using 1 percentdiisobutyl aluminum hydride. The dimers are recovered by distillationand the non-dimers are retained for further isomerization-dimerization.Thedimer product is approximately 30 percent vinylidene C and 70 percentC tri-substituted olefin of formula Example 5 is repeated with mixeddecenes obtained from chlorination and dehydrochlorination of decane.Similar results are obtained.

Example 8 Examples 5 and 6 are repeated with other typical olefinmixtures such as mixed tetradecenes and mixed hexadecenes and with mixedmolecular weight materials such as mixtures of decenes, undecenes,dodecenes, tridecenes, tetradecenes and pentadecenes, hexadecenes,heptadecenes, and octadecenes. Similar results are obtained with thevarious molecular weight materials producing various configurations ofvinylidene olefins and tri-substituted olefins.

Example 9 Example 1 is repeated using 1.0 mol of the olefin which isadded to 5.0 moles of 70 percent (wt.) nitric acid containing 0.2 g.ammonium metavanadate. The temperature is maintained at -60 duringaddition and for an additional two hours. After standing overnight at25, the acid product is collected by ether extraction and purified byextraction with caustic and reacidification. Similar results areobtained.

Example 10 Example 1 is repeated. A mixture of ml. of percent nitricacid and 0.1 g. ammonium metavanadate is put in a three-necked flaskfitted with a stirrer, a condenser, an ice-cooled buret, a droppingfunnel, and a thermometer. The reaction mixture is cooled to 0 and 37.5g. (25.2 mL, 0.4 mole) nitrogen tetroxide and 0.4 mole of the olefinwere added simultaneously during about 3 hours with the temperature keptbelow 4. The mixture is then stirred at 0 for 1.5 hrs. then slowly addedto 24 ml. (0.4 mole) 70 percent (wt.) nitric acid kept at 6065 over a 1hour period. The addition took 1.5 hrs. The mixture is kept at 60 threemore hours, then diluted with water and extracted with ether followed byextraction with caustic and reacidification. Similar desirable resultsare obtained.

I claim:

1. The process of preparing straight chain fatty acids predominantly inthe C to C range, which process is characterized by oxidizing an olefinhaving the formula wherein R methyl radical or straight chain alkylradical having from about 7 to about 18 carbon atoms per radical,

R =straight chain alkyl radical having from about 7 to about 18 carbonatoms per radical,

R =H, methyl radical or straight chain alkyl radical having from about 7to about 18 carbon atoms per radical,

with the proviso that when R is straight chain, R

is methyl,

1 l and carrying out the oxidizing with molecular oxygen,

at a temperature from 75 C. to about 110 C. whereby mainly R1, R2, R3,R1C, R20, R3C and acids are produced.

2. The process of claim 1 wherein the product acids 5 are predominantlyin the C to C range and R and R individually, are straight chain allylradicals having more than 10 but not more than 14 carbon atoms perradical and R is hydrogen.

3. The process of claim 1 wherein the product acids are predominantly inthe C to C range and the R and R straight chain alkyls have more than 10but not more than 14 carbons and R is hydrogen or a straight chain alkylhaving up to 18 carbons.

12 References Cited UNITED STATES PATENTS OTHER REFERENCES Morrison etal.: Organic Chemistry (1959), page 127,

US. Cl. X.R.

P0405" UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.5, 557 9 Dated January 9, 97

Inventor(s) Gene C. Robinson It is certified that error appears in theabove-identified patent and that: said Letters Patent are herebycorrected as shown below:

Column 2, line 17, reads "connection", should read connected Column 5,line 65 reads "pattern, The should read pattern. The Column 6, line 65,reads "virtually as should read virtually twice as Column 8, line 19,reads "eicosesne", should read eicosene Column 11, line 7, reads"allyl", should read alkyl Signed and sealed this 15th day of June 1971.

(SEAL) Attest:

EDWARD M. LETCHER,JR. WILLIAM E. SCHUYLvlR, JR. Attesting OfficerCommissioner of Patents

